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Conformations and Barriers of Haloethyl Radicals (CH_2XCH_2, X = F, Cl, Br, I): Ab Initio Studies

Ihee, Hyotcherl and Zewail, Ahmed H. and Goddard, William A., III (1999) Conformations and Barriers of Haloethyl Radicals (CH_2XCH_2, X = F, Cl, Br, I): Ab Initio Studies. Journal of Physical Chemistry A, 103 (33). pp. 6638-6649. ISSN 1089-5639. doi:10.1021/jp990867n.

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Radicals such as CH_2XCH_2•, where X is a halogen, play an important role in the stereochemical control observed in many chemical reactions. To elucidate the origin of the stereoselectivity, we calculated the structures and potential energy surfaces of the haloethyl radicals (CH_2XCH_2•, X = F, Cl, Br, I) using ab initio quantum mechanics [HF, local MP2, DFT (both B3PW91 and B3LYP)]. We find that the CH_2BrCH_2• and CH_2ICH_2• radicals strongly favor the symmetrically bridged structures while the CH_2ClCH_2• radical leads to similar energy for symmetric bridging and classical structures. (In contrast, X = H and F leads to dramatically different structures). This confirms the Skell hypothesis of symmetric bridging to explain the stereochemical control of the CH_2BrCH_2• and CH_2ICH_2• radicals, indicating that such bridged structures play an important role in the dissociation processes involving CH_2XCH_2• with X = Cl, Br, and I. The trends in the rotational barriers and structural parameters are consistent with hyperconjugation between the singly occupied carbon 2p orbital and the σ^*(C-X) MO. We find that the rotational barrier, bridged structure, and dissociation of the radicals are described much more accurately using DFT (with GGA) than with HF or LMP2.

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Goddard, William A., III0000-0003-0097-5716
Additional Information:© 1999 American Chemical Society. Received: March 12, 1999; In Final Form: June 8, 1999. Publication Date (Web): July 28, 1999. This research was funded (W.A.G.) by the NSF (CHE 95-12279), and a grant (A.Z.) from the Air Force Office of Scientific Research and the Office of Naval Research. The facilities of the MSC are also supported by grants from DOE-ASCI, BP Chemical, ARO-MURI, ARO-DURIP, Owens-Corning, Exxon, Chevron Corp., Dow Chemical, Avery Dennison, Beckman Institute, and Asahi Chemical. H.I. is grateful to Dr. S. Hwang and J. Kua for their technical help.
Funding AgencyGrant Number
NSFCHE 95-12279
Air Force Office of Scientific Research (AFOSR)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Department of Energy (DOE)UNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
Chevron CorporationUNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Issue or Number:33
Record Number:CaltechAUTHORS:20160823-093536856
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Official Citation:Conformations and Barriers of Haloethyl Radicals (CH2XCH2, X = F, Cl, Br, I):  Ab Initio Studies Hyotcherl Ihee, Ahmed H. Zewail, and William A. Goddard III The Journal of Physical Chemistry A 1999 103 (33), 6638-6649 DOI: 10.1021/jp990867n
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:69844
Deposited By: Ruth Sustaita
Deposited On:23 Aug 2016 20:42
Last Modified:11 Nov 2021 04:20

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